US20040192046A1 - Highly selective silicon oxide etching compositions - Google Patents
Highly selective silicon oxide etching compositions Download PDFInfo
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- US20040192046A1 US20040192046A1 US10/817,563 US81756304A US2004192046A1 US 20040192046 A1 US20040192046 A1 US 20040192046A1 US 81756304 A US81756304 A US 81756304A US 2004192046 A1 US2004192046 A1 US 2004192046A1
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- United States
- Prior art keywords
- metal
- solution
- bifluoride
- acid
- silicon oxides
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- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 44
- 238000005530 etching Methods 0.000 title claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims description 41
- 238000000034 method Methods 0.000 claims abstract description 49
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052914 metal silicate Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 43
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 239000004065 semiconductor Substances 0.000 claims description 18
- -1 fluoroborates Chemical compound 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 150000001735 carboxylic acids Chemical class 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000002161 passivation Methods 0.000 claims description 7
- 238000001020 plasma etching Methods 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 125000001477 organic nitrogen group Chemical class 0.000 claims description 3
- 150000003839 salts Chemical group 0.000 claims description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- BZWNJUCOSVQYLV-UHFFFAOYSA-H trifluoroalumane Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Al+3].[Al+3] BZWNJUCOSVQYLV-UHFFFAOYSA-H 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 23
- 239000000243 solution Substances 0.000 description 25
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 13
- 150000008065 acid anhydrides Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001357 Galvanic etching Methods 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 238000010640 amide synthesis reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C11D2111/22—
Definitions
- the present invention relates to etching compositions having reduced water content for the selective removal of silicon oxides from metal surfaces.
- the present invention relates to reduced water content solutions of a bifluoride source compound in a carboxylic acid, and methods for providing selective removal of silicon oxides using these solutions.
- circuitry on a semiconductor chip has to connect with other circuits. These may be chips or display devices, transducers or electromechanical devices. Each of these situations will require the imposition of circuitry to interface the chip to the external environment. This interface is supplied by bonding pads.
- bonding pads are the squares of metal, typically aluminum, generally 100 to 150 microns square, that are connected to the pins of the semiconductor package with bonding wires. Bonding pads are normally positioned near to the chip edge. Toward the end of the semiconductor fabrication process, passivation coatings are applied to protect the fabricated device. Silicon oxide films are typically deposited, often pyrolytically, using layers of oxides such as oxynitride, silicon dioxide, phosphorus-silicate-glass, boron-phosphorus-silicate-glass, and the like.
- the silicon oxide must be removed from the bonding pad so that the fabricated device can interconnect with other circuits.
- An etching composition is typically employed to remove the passivation coating.
- the present invention thus provides an etching composition that can be used to over-etch silicon oxide containing passivating coatings from the metal surfaces of bonding pads without roughing or pitting the surface or dissolving the pad completely, and to etch vias in inter-layer insulation glasses.
- a silicon oxide etching solution in which at least one bifluoride source compound is dissolved in a carboxylic acid solvent and which further includes from about 0.5 to about 3 percent by solution weight of hydrofluoric acid and from about 1 to about 5 percent by solution weight of water, wherein the total bifluoride source compound concentration is between about 1.25 and about 5 moles per kilogram of solvent.
- bifluoride source compounds are ammonium fluoride and ammonium bifluoride, with solutions of ammonium fluoride and ammonium bifluoride in acetic acid being particularly preferred.
- solutions may be prepared by adding acid anhydrides, such as acetic anhydride, to aqueous solutions of ammonium fluoride or ammonium bifluoride so that the acid anhydrides react with the water to dehydrate the solution and form the corresponding carboxylic acids.
- the etching compositions are preferably essentially free of carboxylic acid amides, which is defined as a solution in which the level of any carboxylic acid amide present is insufficient to reduce the etching rate of the composition more than five percent.
- the level of carboxylic acid amide should be undetectable.
- Such etching compositions that are essentially free of carboxylic acid amides may be prepared by the methods described in parent U.S. patent application Ser. No. 10/176,278.
- the etching compositions of the present invention exhibit high selectivity to silicon oxide coatings, and do not corrode underlaying metal layers, even with extended exposure.
- the compositions do not attack metal, and do not promote galvanic etching.
- the present invention thus provides etching compositions that can be used in semiconductor fabrication to remove by over-etching the silicon oxide passivating coatings that are formed on bonding pad surfaces, without roughing or pitting the pad surfaces or otherwise dissolving the pad.
- etching compositions of the present invention which may be used to selectively remove silicon oxides from essentially any metal surface.
- the etching compositions can also be used to open semiconductor vias for subsequent metal deposition, or to remove silicon oxide deposits from bonding pads that form as a consequence of essentially any semiconductor fabrication process step, including reactive ion etching process steps.
- a method for selectively removing silicon oxides from metal surfaces by contacting metal surfaces having silicon oxides thereon with an etching composition according to the present invention for a period of time effective to remove at least a portion of the silicon oxides.
- the methods of the present invention are suitable for use with metal surfaces formed from aluminum, copper, tungsten, tin, titanium, nickel, vanadium, lead and the like. Methods are preferred in which the silicon oxides are essentially completely removed, and methods in which the silicon oxide is removed from a semiconductor bonding pad or to open a via are particularly preferred.
- the etching compositions of the present invention exhibit high selectivity to metal silicates such as titanium silicates and aluminum silicates that are formed by various plasma etching processes, and do not attack underlying metal layers or organic dielectric coatings, even with extended exposure. Therefore, according to yet another aspect of the present invention, a method is provided for selectively removing metal silicates from metal surfaces by contacting the surfaces with an etching composition according to the present invention for a period of time effective to remove at least a portion of the silicates. Again, methods are preferred in which the metal silicates are essentially completely removed.
- the metal surfaces include metal surfaces at least partially coated with at least one organic dielectric compound.
- film refers to the various oxides, including silicon dioxides that are formed by various semiconductor layer or coating fabrication processes, including plasma etching and plasma deposition processes.
- the etching compositions of the present invention are solutions of at least one bifluoride source compound, hydrofluoric acid and water in a carboxylic acid solvent.
- the carboxylic acid solvent may be a single carboxylic acid or a mixture of two or more carboxylic acids.
- carboxylic acids are defined as including mono-, di- and tricarboxylic acids; esters, amides and any unreacted residual anhydrides thereof; as well as amino acids and halogenated carboxylic acids.
- Monocarboxylic acids are preferred.
- carboxylic acid compounds having from zero to five carbon atoms in addition to the carboxylate carbon(s) are preferred, with acetic acid being most preferred. More than one carboxylic acid may be used, but, as is readily understood by those skilled in the art, when an acidic proton is needed to form the biflouride species, at least one carboxylic acid must contain an acidic proton.
- the bifluoride source compounds of the present invention form bifluoride species [(HF 2 ) ⁇ ] when dissolved in the carboxylic acids of the inventive etching compositions.
- Bifluoride source compounds that form bifluoride species in this manner are readily identified by those skilled in the art without undue experimentation. Examples of such compounds include ammonium fluoride, ammonium bifluoride, fluoroborates, fluoroboric acid, tin bifluoride, antimony fluoride, tetrabutylammonium tetrafluoroborate, aluminum hexafluoride, and the like. More than one carboxylic acid or bifluoride source compound may be employed.
- Hydrogen fluoride acid addition and quaternary salts of organic nitrogen-containing compounds are also bifluoride source compounds. These include acid addition and quaternary salts of aliphatic amines, aromatic amines and nitrogen-containing heterocyclic compounds.
- the amines include primary, secondary and tertiary amines.
- Ammonium fluoride and ammonium bifluoride are among the preferred bifluoride source compounds. Two moles of ammonium fluoride combine with one mole of a monocarboxylic acid, such as acetic acid, to form one mole of ammonium bifluoride and one mole of ammonium acetate (a carboxylic acid species), as shown below:
- a monocarboxylic acid such as acetic acid
- Silicon oxide etching rates increase as the bifluoride source compound concentration increases, without adversely affecting the selectivity for silicon oxides over metals.
- a total bifluoride source compound concentration between about 1.75 and about 3.75 moles per kilogram of solvent is preferred.
- Examples of etching compositions of the present invention containing ammonium fluoride and acetic acid include compounds containing from about 5% to about 14% by solution weight ammonium fluoride. From about 7%, to about 11% by solution weight ammonium fluoride is preferred, with about 9% by solution weight being more preferred.
- compositions will also contain from about 1.5% to about 5% by solution weight water, with from about 2% to about 3% by solution weight water being preferred, and from about 0.5% to about 3% by solution weight hydrofluoric acid, with from about 1% to about 2.5 % by solution weight hydrofluoric acid being preferred.
- the etchant compositions of the present invention are prepared by combining a stoichiometric quantities of the one or more carboxylic acids and the one or more bifluoride source compounds, which are mixed until the one or more bifluoride source compounds dissolve in the carboxylic acid(s).
- the water and hydrofluoric acid are then added with further mixing until all components dissolve.
- the hydrofluoric acid is typically added as an aqueous 49% hydrofluoric acid solution.
- one or more acid anhydrides are added to an aqueous solution of at least one bifluoride source compounds to form upon contact with water at least one of the carboxylic acids intended for use in the etching compositions.
- One or more of the carboxylic acids may be present in the aqueous bifluoride source compound solution, provided that enough acid anhydride is stoichiometrically employed to attain the desired reduction in water content.
- This combination is then mixed until the acid anhydride(s) hydrolyze(s) and the bifluoride source compound(s) dissolve(s).
- Aqueous 49% hydrofluoric acid and any further water are then added with further mixing until all components dissolve.
- compositions containing more than one carboxylic acid more than one acid anhydride may be used to dehydrate the aqueous bifluoride source compound solution, to form carboxylic acids intended for use in the etching composition upon contact with the water, even when the corresponding carboxylic acids are already present in the aqueous solution.
- one of the intended carboxylic acids may be added as an acid anhydride, while the other(s) are present as carboxylic acid(s) in the aqueous solution.
- acetic anhydride is used, and so forth.
- concentration of the bifluoride source compound in the aqueous solution is selected to provide the desired concentration of bifluoride source compounds and water in the inventive composition upon reaction of the acid anhydride with the water to form the carboxylic acid solvent.
- reaction is exothermic, requiring the removal of, rather than the addition of, thermal energy.
- the reaction runs to completion within about six hours.
- the conditions and apparatus for preparing the compositions of the present invention by this method are essentially conventional and require no further description.
- the preparation of a solution of ammonium fluoride in acetic acid by adding acetic anhydride to an aqueous solution of ammonium fluoride is preferably performed under controlled temperature conditions.
- the reaction temperature is preferably maintained below 40° C. to avoid the formation of acetamide as a by-product formed by a reaction that occurs between the ammonium moiety and the anhydride at higher temperatures.
- a temperature between about 10 and about 40° C. is preferred, with a temperature between about 20 and about 30° C. even more preferred.
- the acid anhydride addition to the aqueous bifluoride source compound should be slowly apportioned to allow the initial reaction between the water and the anhydride to occur before adding additional anhydride. This will maximize dehydration of the solution and, for reactions between ammonium fluoride and acid anhydrides, minimize acid amide formation by preventing excessive heat from being locally generated that would otherwise result in over-heating of the reaction mixture.
- compositions of the present invention prepared by combining ammonium fluoride with hydrofluoric acid, acetic acid and/or acetic anhydride and water to form ammonium bifluoride and ammonium acetate can be prepared by the method disclosed in WO 00/58,208.
- stoichiometric quantities of anhydrous gaseous or liquid hydrogen fluoride and anhydrous gaseous or liquid ammonia can be added to a stoichiometric amount of a carboxylic acid to obtain the mixture of ionic species that would otherwise form by reacting ammonium fluoride with a carboxylic acid, i.e., ammonium bifluoride and ammonium carboxylate, and then adding hydrofluoric acid.
- Employment of the proper stoichiometric quantities of hydrogen fluoride, ammonia gas and carboxylic acid in the processes described by this publication will result in the desired concentrations of ammonium bifluoride, ammonium carboxylate and hydrofluoric acid.
- the process permits the concentrations of ammonium fluoride, carboxylic acid, hydrofluoric acid and water, to be prepared with pinpoint accuracy.
- the methods of the present invention for selectively removing silicon oxides from metal surfaces are performed by employing the inventive compositions in conventional etching and cleaning processes that require no further description.
- the processes are typically carried out at temperatures between about 20 and about 50° C., and preferably from about 20 to about 30° C.
- the methods of the present invention may be used to selectively remove silicon oxides from essentially any metal surface.
- inventive methods and compositions may be used to remove silicon oxides from semiconductor bonding pads, including silicon oxide coating layers that have been applied as passivation coatings, and silicon oxide deposits that have formed during semiconductor fabrication process steps, including the process steps of reactive ion etching.
- the compositions and methods may be used to remove silicon oxides to open semiconductor vias for subsequent metal deposition.
- compositions of the present invention are ideally selective in the removal of silicon oxides from aluminum surfaces, and may thus be used not only to remove silicon oxides from aluminum bonding pads, but also to remove the silicon oxide deposits that form on the anodized aluminum parts of sputtering equipment and gaseous deposition equipment used for the reactive ion etching of semiconductor devices.
- the metal silicates typically form on metal surfaces as a consequence of plasma etching processes.
- aluminum silicates or titanium silicates form on aluminum and titanium surfaces, respectively.
- the compositions of the present invention will remove the metal silicates without attacking the underlying metal.
- the compositions will also not attack any organic dielectric coating that may be formed on the metal surfaces.
- a 9.4 lb. quantity of an etching composition according to the present invention was prepared by adding 1.078 lbs. of ammonium fluoride powder to 7.097 lbs. of 99% acetic acid with mixing. Mixing continued for two hours, after which 0.224 lbs. of aqueous 49% hydrofluoric acid and 0.18 lbs deionized water was added. Mixing continued for thirty minutes, after which the resulting solution was bottled.
- the final composition was 11.58% ammonium fluoride, 2.39% hydrofluoric acid, 1.91% water and 84% acetic acid.
- the etching composition was contacted with the aluminum bonding pads of a semiconductor device that were coated with silicon oxides as a passivation layer.
- the device included exposed aluminum surfaces.
- the etching solution was contacted until the silicon oxides were completely removed from the bonding pad. There was no detectable removal of aluminum from the bonding pads or the exposed aluminum surfaces.
- Example 1 was repeated using 48 lbs. ammonium fluoride, 356 lbs. 99% acetic acid, 12 lbs. aqueous 49% hydrofluoric acid and 8.5 lbs. water.
Abstract
Description
- The present application is a Continuation-In-Part of U.S. patent application Ser. No. 10/176,278 filed Jun. 20, 2002.
- The present invention relates to etching compositions having reduced water content for the selective removal of silicon oxides from metal surfaces. In particular, the present invention relates to reduced water content solutions of a bifluoride source compound in a carboxylic acid, and methods for providing selective removal of silicon oxides using these solutions.
- The circuitry on a semiconductor chip has to connect with other circuits. These may be chips or display devices, transducers or electromechanical devices. Each of these situations will require the imposition of circuitry to interface the chip to the external environment. This interface is supplied by bonding pads.
- Physically, bonding pads are the squares of metal, typically aluminum, generally 100 to 150 microns square, that are connected to the pins of the semiconductor package with bonding wires. Bonding pads are normally positioned near to the chip edge. Toward the end of the semiconductor fabrication process, passivation coatings are applied to protect the fabricated device. Silicon oxide films are typically deposited, often pyrolytically, using layers of oxides such as oxynitride, silicon dioxide, phosphorus-silicate-glass, boron-phosphorus-silicate-glass, and the like.
- Following deposition the silicon oxide must be removed from the bonding pad so that the fabricated device can interconnect with other circuits. An etching composition is typically employed to remove the passivation coating.
- Conventional passivation etchants contain ammonium fluoride, acetic acid, water and additional additives such as ethylene glycol or aluminum acetate. Current processes seek to over-etch the bonding pads to ensure complete elimination of the silicon oxide passivating coating. Over-etching with current products results in significant roughing and pitting of the bonding pad surfaces, creating poor contact points to the detriment of device reliability because current products also attack underlying metal surfaces. The products are known to dissolve pads completely, increasing the manufacturing yield loss.
- There exists a need for a selective silicon oxide passivation coating etchant that does not attack underlying metal surfaces.
- This need is met by the present invention. It has now been discovered that products containing bifluoride species will etch silicon oxide films without attacking or corroding underlying metals, including aluminum, even with extended exposure when the water content is kept to a minimum. It has further been discovered that minor amounts of water and hydrofluroric acid, when added to bifluoride species, improve the selectivity of etching compositions for silicon over aluminum to the extent that no appreciable corrosion or reduction of aluminum film thickness occurs upon prolonged exposure. Until now, it was believed that the presence of any hydrofluoric acid was detrimental to such etch selectivity. The present invention thus provides an etching composition that can be used to over-etch silicon oxide containing passivating coatings from the metal surfaces of bonding pads without roughing or pitting the surface or dissolving the pad completely, and to etch vias in inter-layer insulation glasses.
- Therefore, according to one aspect of the present invention, a silicon oxide etching solution is provided in which at least one bifluoride source compound is dissolved in a carboxylic acid solvent and which further includes from about 0.5 to about 3 percent by solution weight of hydrofluoric acid and from about 1 to about 5 percent by solution weight of water, wherein the total bifluoride source compound concentration is between about 1.25 and about 5 moles per kilogram of solvent.
- Among the preferred bifluoride source compounds are ammonium fluoride and ammonium bifluoride, with solutions of ammonium fluoride and ammonium bifluoride in acetic acid being particularly preferred. These solutions may be prepared by adding acid anhydrides, such as acetic anhydride, to aqueous solutions of ammonium fluoride or ammonium bifluoride so that the acid anhydrides react with the water to dehydrate the solution and form the corresponding carboxylic acids.
- The etching compositions are preferably essentially free of carboxylic acid amides, which is defined as a solution in which the level of any carboxylic acid amide present is insufficient to reduce the etching rate of the composition more than five percent. Preferably, the level of carboxylic acid amide should be undetectable. Such etching compositions that are essentially free of carboxylic acid amides may be prepared by the methods described in parent U.S. patent application Ser. No. 10/176,278.
- The etching compositions of the present invention exhibit high selectivity to silicon oxide coatings, and do not corrode underlaying metal layers, even with extended exposure. The compositions do not attack metal, and do not promote galvanic etching.
- The present invention thus provides etching compositions that can be used in semiconductor fabrication to remove by over-etching the silicon oxide passivating coatings that are formed on bonding pad surfaces, without roughing or pitting the pad surfaces or otherwise dissolving the pad. However, this is but one use for the etching compositions of the present invention, which may be used to selectively remove silicon oxides from essentially any metal surface. For example, the etching compositions can also be used to open semiconductor vias for subsequent metal deposition, or to remove silicon oxide deposits from bonding pads that form as a consequence of essentially any semiconductor fabrication process step, including reactive ion etching process steps.
- Therefore, according to another aspect of the present invention, a method is provided for selectively removing silicon oxides from metal surfaces by contacting metal surfaces having silicon oxides thereon with an etching composition according to the present invention for a period of time effective to remove at least a portion of the silicon oxides. The methods of the present invention are suitable for use with metal surfaces formed from aluminum, copper, tungsten, tin, titanium, nickel, vanadium, lead and the like. Methods are preferred in which the silicon oxides are essentially completely removed, and methods in which the silicon oxide is removed from a semiconductor bonding pad or to open a via are particularly preferred.
- It has further been discovered that the etching compositions of the present invention exhibit high selectivity to metal silicates such as titanium silicates and aluminum silicates that are formed by various plasma etching processes, and do not attack underlying metal layers or organic dielectric coatings, even with extended exposure. Therefore, according to yet another aspect of the present invention, a method is provided for selectively removing metal silicates from metal surfaces by contacting the surfaces with an etching composition according to the present invention for a period of time effective to remove at least a portion of the silicates. Again, methods are preferred in which the metal silicates are essentially completely removed. The metal surfaces include metal surfaces at least partially coated with at least one organic dielectric compound.
- In addition, for purposes of the present invention, the terms “film,” “coating” and “layer” are used interchangeably, regardless of whether each is applied as a deliberate step in a process of semiconductor fabrication or as a consequence of the performance of a semiconductor fabrication processing step. “Silicon oxides” refer to the various oxides, including silicon dioxides that are formed by various semiconductor layer or coating fabrication processes, including plasma etching and plasma deposition processes.
- The etching compositions of the present invention are solutions of at least one bifluoride source compound, hydrofluoric acid and water in a carboxylic acid solvent. The carboxylic acid solvent may be a single carboxylic acid or a mixture of two or more carboxylic acids. For purposes of the present invention, carboxylic acids are defined as including mono-, di- and tricarboxylic acids; esters, amides and any unreacted residual anhydrides thereof; as well as amino acids and halogenated carboxylic acids. Monocarboxylic acids are preferred. In addition, carboxylic acid compounds having from zero to five carbon atoms in addition to the carboxylate carbon(s) are preferred, with acetic acid being most preferred. More than one carboxylic acid may be used, but, as is readily understood by those skilled in the art, when an acidic proton is needed to form the biflouride species, at least one carboxylic acid must contain an acidic proton.
- The bifluoride source compounds of the present invention form bifluoride species [(HF2)−] when dissolved in the carboxylic acids of the inventive etching compositions. Bifluoride source compounds that form bifluoride species in this manner are readily identified by those skilled in the art without undue experimentation. Examples of such compounds include ammonium fluoride, ammonium bifluoride, fluoroborates, fluoroboric acid, tin bifluoride, antimony fluoride, tetrabutylammonium tetrafluoroborate, aluminum hexafluoride, and the like. More than one carboxylic acid or bifluoride source compound may be employed. Hydrogen fluoride acid addition and quaternary salts of organic nitrogen-containing compounds are also bifluoride source compounds. These include acid addition and quaternary salts of aliphatic amines, aromatic amines and nitrogen-containing heterocyclic compounds. The amines include primary, secondary and tertiary amines.
- Ammonium fluoride and ammonium bifluoride are among the preferred bifluoride source compounds. Two moles of ammonium fluoride combine with one mole of a monocarboxylic acid, such as acetic acid, to form one mole of ammonium bifluoride and one mole of ammonium acetate (a carboxylic acid species), as shown below:
- 2NH4F+CH3COOH→(NH4)+(HF2)−+(CH3COO−)(NH4 +)
- This is shown to illustrate how bifluoride species are formed in a carboxylic acid solution, and is not meant in any way to limit the invention to combinations of NH4F and acetic acid. However, this is among the particularly preferred embodiments of the present invention. An equally preferred embodiment directly dissolves ammonium bifluoride in one or more carboxylic acids.
- Silicon oxide etching rates increase as the bifluoride source compound concentration increases, without adversely affecting the selectivity for silicon oxides over metals. A total bifluoride source compound concentration between about 1.75 and about 3.75 moles per kilogram of solvent is preferred. Examples of etching compositions of the present invention containing ammonium fluoride and acetic acid include compounds containing from about 5% to about 14% by solution weight ammonium fluoride. From about 7%, to about 11% by solution weight ammonium fluoride is preferred, with about 9% by solution weight being more preferred. Such compositions will also contain from about 1.5% to about 5% by solution weight water, with from about 2% to about 3% by solution weight water being preferred, and from about 0.5% to about 3% by solution weight hydrofluoric acid, with from about 1% to about 2.5 % by solution weight hydrofluoric acid being preferred.
- The etchant compositions of the present invention are prepared by combining a stoichiometric quantities of the one or more carboxylic acids and the one or more bifluoride source compounds, which are mixed until the one or more bifluoride source compounds dissolve in the carboxylic acid(s). The water and hydrofluoric acid are then added with further mixing until all components dissolve. The hydrofluoric acid is typically added as an aqueous 49% hydrofluoric acid solution.
- Alternatively, one or more acid anhydrides are added to an aqueous solution of at least one bifluoride source compounds to form upon contact with water at least one of the carboxylic acids intended for use in the etching compositions. One or more of the carboxylic acids may be present in the aqueous bifluoride source compound solution, provided that enough acid anhydride is stoichiometrically employed to attain the desired reduction in water content. This combination is then mixed until the acid anhydride(s) hydrolyze(s) and the bifluoride source compound(s) dissolve(s). Aqueous 49% hydrofluoric acid and any further water are then added with further mixing until all components dissolve.
- For compositions containing more than one carboxylic acid, more than one acid anhydride may be used to dehydrate the aqueous bifluoride source compound solution, to form carboxylic acids intended for use in the etching composition upon contact with the water, even when the corresponding carboxylic acids are already present in the aqueous solution. Alternatively, one of the intended carboxylic acids may be added as an acid anhydride, while the other(s) are present as carboxylic acid(s) in the aqueous solution.
- Thus, for etching compositions containing acetic acid, acetic anhydride is used, and so forth. The concentration of the bifluoride source compound in the aqueous solution is selected to provide the desired concentration of bifluoride source compounds and water in the inventive composition upon reaction of the acid anhydride with the water to form the carboxylic acid solvent.
- The reaction is exothermic, requiring the removal of, rather than the addition of, thermal energy. The reaction runs to completion within about six hours. The conditions and apparatus for preparing the compositions of the present invention by this method are essentially conventional and require no further description.
- The preparation of a solution of ammonium fluoride in acetic acid by adding acetic anhydride to an aqueous solution of ammonium fluoride is preferably performed under controlled temperature conditions. In particular, the reaction temperature is preferably maintained below 40° C. to avoid the formation of acetamide as a by-product formed by a reaction that occurs between the ammonium moiety and the anhydride at higher temperatures. A temperature between about 10 and about 40° C. is preferred, with a temperature between about 20 and about 30° C. even more preferred.
- The formation of acetamide is undesirable because it slows the etching rate and tends to fog silicon wafer surfaces. Reaction temperatures should be controlled for essentially any reaction between ammonium fluoride and an acid anhydride to prevent the formation of undesirable acid amides that in general slow the rate of etching.
- The acid anhydride addition to the aqueous bifluoride source compound should be slowly apportioned to allow the initial reaction between the water and the anhydride to occur before adding additional anhydride. This will maximize dehydration of the solution and, for reactions between ammonium fluoride and acid anhydrides, minimize acid amide formation by preventing excessive heat from being locally generated that would otherwise result in over-heating of the reaction mixture.
- In yet another alternate method, the compositions of the present invention prepared by combining ammonium fluoride with hydrofluoric acid, acetic acid and/or acetic anhydride and water to form ammonium bifluoride and ammonium acetate can be prepared by the method disclosed in WO 00/58,208. For example, stoichiometric quantities of anhydrous gaseous or liquid hydrogen fluoride and anhydrous gaseous or liquid ammonia can be added to a stoichiometric amount of a carboxylic acid to obtain the mixture of ionic species that would otherwise form by reacting ammonium fluoride with a carboxylic acid, i.e., ammonium bifluoride and ammonium carboxylate, and then adding hydrofluoric acid. Employment of the proper stoichiometric quantities of hydrogen fluoride, ammonia gas and carboxylic acid in the processes described by this publication will result in the desired concentrations of ammonium bifluoride, ammonium carboxylate and hydrofluoric acid. Furthermore, the process permits the concentrations of ammonium fluoride, carboxylic acid, hydrofluoric acid and water, to be prepared with pinpoint accuracy.
- The methods of the present invention for selectively removing silicon oxides from metal surfaces are performed by employing the inventive compositions in conventional etching and cleaning processes that require no further description. The processes are typically carried out at temperatures between about 20 and about 50° C., and preferably from about 20 to about 30° C.
- As noted above, the methods of the present invention may be used to selectively remove silicon oxides from essentially any metal surface. Thus, the inventive methods and compositions may be used to remove silicon oxides from semiconductor bonding pads, including silicon oxide coating layers that have been applied as passivation coatings, and silicon oxide deposits that have formed during semiconductor fabrication process steps, including the process steps of reactive ion etching. In addition, the compositions and methods may be used to remove silicon oxides to open semiconductor vias for subsequent metal deposition. The compositions of the present invention are ideally selective in the removal of silicon oxides from aluminum surfaces, and may thus be used not only to remove silicon oxides from aluminum bonding pads, but also to remove the silicon oxide deposits that form on the anodized aluminum parts of sputtering equipment and gaseous deposition equipment used for the reactive ion etching of semiconductor devices.
- The methods of the present invention for selectively removing metal silicates from metal surfaces similarly employed the inventive compositions in conventional cleaning processes that require no further description. These processes are also typically carried out at essentially the same temperatures.
- The metal silicates typically form on metal surfaces as a consequence of plasma etching processes. Typically, aluminum silicates or titanium silicates form on aluminum and titanium surfaces, respectively. The compositions of the present invention will remove the metal silicates without attacking the underlying metal. The compositions will also not attack any organic dielectric coating that may be formed on the metal surfaces.
- The following non-limiting examples are presented to further illustrate the present invention.
- A 9.4 lb. quantity of an etching composition according to the present invention was prepared by adding 1.078 lbs. of ammonium fluoride powder to 7.097 lbs. of 99% acetic acid with mixing. Mixing continued for two hours, after which 0.224 lbs. of aqueous 49% hydrofluoric acid and 0.18 lbs deionized water was added. Mixing continued for thirty minutes, after which the resulting solution was bottled.
- The final composition was 11.58% ammonium fluoride, 2.39% hydrofluoric acid, 1.91% water and 84% acetic acid.
- The etching composition was contacted with the aluminum bonding pads of a semiconductor device that were coated with silicon oxides as a passivation layer. The device included exposed aluminum surfaces. The etching solution was contacted until the silicon oxides were completely removed from the bonding pad. There was no detectable removal of aluminum from the bonding pads or the exposed aluminum surfaces.
- Example 1 was repeated using 48 lbs. ammonium fluoride, 356 lbs. 99% acetic acid, 12 lbs. aqueous 49% hydrofluoric acid and 8.5 lbs. water.
- In this disclosure, there are shown and described only the preferred embodiments of the invention. It is to be understood that the invention is capable of use in various other combinations and environments and is capable of changes or modifications within the scope of the inventive concept as expressed herein.
Claims (23)
Priority Applications (5)
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US10/817,563 US7192860B2 (en) | 2002-06-20 | 2004-04-02 | Highly selective silicon oxide etching compositions |
PCT/US2005/010958 WO2005096747A2 (en) | 2004-04-02 | 2005-03-31 | Highly selective silicon oxide etching compositions |
JP2007506575A JP2007532006A (en) | 2004-04-02 | 2005-03-31 | Highly selective silicon oxide etching composition |
EP05731386A EP1735825A2 (en) | 2004-04-02 | 2005-03-31 | Highly selective silicon oxide etching compositions |
TW094110737A TW200617147A (en) | 2004-04-02 | 2005-04-04 | Highly selective silicon oxide etching compositions |
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US10/176,278 US20030235986A1 (en) | 2002-06-20 | 2002-06-20 | Silicon oxide etching compositions with reduced water content |
US10/817,563 US7192860B2 (en) | 2002-06-20 | 2004-04-02 | Highly selective silicon oxide etching compositions |
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US10/176,278 Continuation-In-Part US20030235986A1 (en) | 2002-06-20 | 2002-06-20 | Silicon oxide etching compositions with reduced water content |
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US7192860B2 US7192860B2 (en) | 2007-03-20 |
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EP (1) | EP1735825A2 (en) |
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Cited By (3)
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US20060046513A1 (en) * | 2004-09-02 | 2006-03-02 | Shea Kevin R | Selective etching of oxides to metal nitrides and metal oxides |
US20100239818A1 (en) * | 2009-03-18 | 2010-09-23 | Seung Jin Lee | Textured silicon substrate and method |
EP2463410A3 (en) * | 2010-12-13 | 2016-11-16 | Rohm and Haas Electronic Materials LLC | Electrochemical etching of semiconductors |
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WO2007044447A2 (en) * | 2005-10-05 | 2007-04-19 | Advanced Technology Materials, Inc. | Composition and method for selectively etching gate spacer oxide material |
KR100741991B1 (en) * | 2006-06-29 | 2007-07-23 | 삼성전자주식회사 | Silicon oxide etching solution and method of forming contact hole using the same |
CA2716641A1 (en) * | 2008-02-29 | 2009-09-03 | Mallinckrodt Baker, Inc. | Microelectronic substrate cleaning compositions |
JP2012238849A (en) | 2011-04-21 | 2012-12-06 | Rohm & Haas Electronic Materials Llc | Improved polycrystalline texturing composition and method |
JP6136186B2 (en) * | 2012-10-16 | 2017-05-31 | 日立化成株式会社 | Liquid composition |
EP3978585A1 (en) | 2020-09-30 | 2022-04-06 | Imec VZW | Aqueous solution for etching silicon oxide |
JP2023112748A (en) * | 2022-02-02 | 2023-08-15 | 関東化学株式会社 | Etching liquid composition, method for manufacturing etching liquid composition, and etching method using the etching liquid composition |
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- 2005-03-31 WO PCT/US2005/010958 patent/WO2005096747A2/en not_active Application Discontinuation
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EP1735825A2 (en) | 2006-12-27 |
WO2005096747A2 (en) | 2005-10-20 |
WO2005096747A3 (en) | 2006-03-30 |
JP2007532006A (en) | 2007-11-08 |
US7192860B2 (en) | 2007-03-20 |
TW200617147A (en) | 2006-06-01 |
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